Iron and phosphorus containing compositions



United States Patent 3,398,100 IRON AND PHOSPHORUS CONTAINING COMPOSITIONS Harold F. Christmann, Houston, Tex., assignor to Petro- Tex Chemical Corporation, Houston, Tex., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 377,091, June 22, 1964. This application May 31, 1966, Ser. No. 553,660 The portion of the term of the patent subsequent to Aug. 29, 1983, has been disclaimed 16 Claims. (Cl. 252-435) ABSTRACT OF THE DISCLOSURE New compositions of matter comprising iron, phosphorus and at least one other metallic element other than iron, especially magnesium, zinc, cobalt, nickel or mixtures thereof. The phosphorus is present in an amount of from .002 to 0.35 atom of phosphorus per atom of iron and the magnesium, zinc, cobalt and nickel are present in the total amount of from .05 to 2 atoms per atom of iron. The compositions comprise oxygen and preferably are at least partially crystalline. Ferrites are preferred. Compositions are useful such as for catalysts for oxidative dehydrogenation and as pigments.

This application is a continuation-in-part of Ser. No. 377,091 entitled Production of Unsaturated Compounds filed June 22, 1964, now Patent No. 3,270,080.

In copending applications it has been disclosed that an improved process for the dehydrogenation of organic compounds is provided by contacting the organic compound at an elevated temperature with oxygen in the presence of certain catalysts containing iron, and at least one of a certain group of metals. Although excellent results are obtained with the catalysts of the copending applications, it is an object of this invention to provide further improved catalysts. One of the principal objects of this invention is to improve the life of the catalyst. Another object is to provide a more rugged catalyst. Still other objects are to increase the conversion, selectivity and yield of the catalyst, as well as to prevent coke formation on the catalyst.

The catalysts of this invention comprise iron, phosphorus and as a third component at least one metal selected from the group consisting of magnesium, zinc, cobalt, nickel, and mixtures thereof. The phosphorus should be present in an amount of from or about .002 to 0.25 or 0.35 atom of phosphorus per atom of iron in the catalyst, and preferably will be between about .005 and 0.20 atom of phosphorus per atom of iron. The total number of atoms selected from the group consisting of magnesium, zinc, cobalt and nickel should be from about .05 to 2.0 total atoms per atom of iron and preferably will be from or about .20 to 1.0 total atoms per atom of iron, with a particularly preferred ratio of .35 to .6 total atoms per atom of iron. The atoms of phosphorus will generally be present in an amount from or about 0.2 to 16 weight percent phosphorus, based on the total weight of the atoms of iron, magnesium, zinc, cobalt, nickel and combinations thereof.

The catalyst will also contain oxygen, but the ratio of oxygen to the remaining atoms is variable. The ratio of oxygen to iron will generally be within the range of about 0.5 to 10 atoms of oxygen per atom of iron, but this ratio may be somewhat higher or lower.

One of the principal benefits obtained by the incorporation of phosphorus in the catalyst is the increased life of the catalyst. Although the catalyst described above conice taining iron and at least one metal selected from the group consisting of magnesium, zinc, cobalt, nickel and mixtures or combinations thereof produce high yields of unsaturated product, frequently these catalysts do not have as long a catalyst life as is desired. Of course, catalyst life is one of the most important criteria in the selection of catalysts. It has been found that the presence of phophorun in critical amounts in the catalyst for some reason stabilizes the catalyst. The high initial yields obtained with the modified catalyst is maintained for prolonged periods of time, and the phosphorus modified catalyst has much higher physical strength.

Especially preferred as iron catalysts to be modified according to the present invention are the ferrites. The ferrites are known commercial products with numerous uses such as for high temperature pigments. The ferrites comprise iron combined in a crystalline structure with at least one other metal and oxygen. The ferrite structure may be determined by X-ray diffraction. Quite often the ferrites will exhibit electrical semi-conductivity and may be magnetic. Examples of ferrites to be modified according to this invention are magnesium ferrite, Zinc ferrite, cobalt ferrite and nickel ferrite. Mixed ferrites have also given excellent results, for example, iron-magnesium-zinc ferrite, iron-magnesium-nickel ferrite, iron-magnesiumcobalt ferrite, iron-zinc-nickel ferrite, and iron-zinc-cobalt ferrite.

Although organic compounds generally may be dehydrogenated with the compositions of this invention, the compositions are most advantageously used for the dehydrogenation of hydrocarbons. Hydrocarbons to be dehydrogenated according to the process of this invention are hydrocarbons of 4 to 7 or 8 carbon atoms and preferably are aliphatic hydrocarbons selected from the group consisting of saturated hydrocarbons, monoolefins, d-iOlefins and mixtures thereof of 4 to 5 or 6 carbon atoms having a straight chain of at least four carbon atoms and cycloaliphatics. Examples of preferred feed materials are butene-l, cis-butene-Z, trans-butene-2, Z-methyIbutene-l, 2-methylbutene-2, 2-methylbutene-3, n-butane, butadiene- 1,3, methyl butane, 2-methylphentene-1, cyclohexene, 2-methylpentene-2 and mixtures thereof. For example, n-butane may be converted to a mixture of butene-l and butene-Z or may be converted to a mixture of butene-l, butene-2 and/ or butadiene-1,3. A mixture of n-butane and butene-2 may be converted to butadiene-1,3 or to a mixture of butadiene-1,3 together with some butene-Z and butene-l. Vinyl acetylene may be present as a product, particularly when butadiene-1,3 is used as a rfeedstock. Thus, the compositions of this invention are useful in converting hydrocarbons to less saturated hydrocarbons of the same number of carbon atoms. Particularly preferred products are butadiene-1,3 and isoprene. Useful feeds may be mixed hydrocarbon streams such as refinery streams, or the olefin containing hydrocarbon mixture obtained as the product from the dehydrogenation of hydrocarbons. In the production of gasoline from higher hydrocarbons by either thermal or catalytic cracking a hydro carbon stream containing predominantly hydrocarbons of 4 carbon atoms may be produced and may comprise a mixture of butenes together with butadiene, butane, isobutane, isobutylene and other ingredients in minor amounts. These and other refinery by-products which contain normal, ethylenically unsaturated hydrocarbons are useful as starting materials. Although various mixtures of hydrocarbons are useful, the preferred hydrocarbon feed contains at least 50 Weight percent of a hydrocarbon selected from the group consisting of butene-l, butene-2, n-butane, butadiene 1,3, 2 methylbutene 1, 2 methylbutene-Z, 2-methylbutene-3 and mixtures thereof, and more preferably contains at least weight percent of one or more of these hydrocarbons (with both of these percentages being based on the total weight of the organic composition of the feed to the reactor). Any remainder may be, for example, essentially aliphatic hydrocarbons. This invention is particularly useful to provide a process whereby the major product of the hydrocarbon converted is a dehydrogenated hydrocarbon product having the same number of carbon atoms as the hydrocarbon fed.

When employing the compositions for oxidative dehydrogenation, oxygen will be present in the reaction zone in an amount within the range of 0.2 to 2.5 mols of oxygen per mol of organic compound such as a hydrocarbon to be dehydrogenated. Generally, better results may be obtained if the oxygen concentration is maintained between about 0.25 and about 1.6 mols of oxygen per mol of hydrocarbon to be dehydrogenated,'such as between 0.35 and 1.2 mols of oxygen. The oxygen may be fed to the reactor as pure oxygen, as air, as oxygenenriched air, oxygen mixed with diluents and so forth.

Based on the total gaseous mixture entering the reactor, the oxygen ordinarily will be present in an amount from about 0.5 to 25 volume percent of the total gaseous rnix ture, and more usually will be present in an amount from about 1 to volume percent of the total. The total amount of oxygen utilized may be introduced into the gaseous mixture entering the catalytic zone or sometimes it has been found desirable to add the oxygen in increments, such as to different sections of the reactor. The oxygen may be added directly to the reactor or it may be premixed, for example, with a diluent or steam.

The temperature for the dehydrogenation reaction will be greater than 250 C., such as greater than about 300 C. or 375 C. Excellent results are obtained within the range of 300 C. to 625 C., and preferably from or about 325 C. to or about 550 C. The temperatures are measured at the maximum temperature in the reactor. An advantage of this invention is that lower temperatures of dehydrogenation may be utilized than are possible in conyentional dehydrogenation processes. Another advantage is that large quantities of heat do not have to be added to the reaction as was previously required.

The dehydrogenation reaction may be carried out at atmospheric pressure, superatmospheric pressure or at subatmospheric pressure. The total pressure of the system will normally be about or in excess of atmospheric pressure, although sub-atmospheric pressure may also desirably be used. Generally, the total pressure will be between about 4 p.s.i.a. and about 100 or 125 p.s.i.a. Preferably the total pressure will be less than about 75 p.s.i.a. and excellent results are obtained at about atmospheric pressure.

The initial partial pressure of the organic compound such as a hydrocarbon to be dehydrogenated will preferably be equivalent to less than one-half atmosphere at a total pressure of one atmosphere. Generally the combined partial pressure of the hydrocarbon to be dehydrogenated together with the oxygen will also be equivalent to less than one-half atmosphere at a total pressure of one atmosphere. Preferably, the initial partial pressure of the hydrocarbon to be dehydrogenated will be equivalent to no greater than one-third atmosphere or no greater than onefifth atmosphere at a total pressure of one atmosphere. Also, preferably the initial partial pressure of the combined hydrocarbon to be dehydrogenated plus the oxygen will be equivalent to no greater than one-third or no greater than one-fifth atmosphere at a total pressure of one atmosphere. Reference to the initial partial pressure of the hydrocarbon to be dehydrogenated means the partial pressure of the hydrocarbon as it first contacts the catalytic particles. An equivalent partial pressure at a total pressure of one atmosphere means that one atmosphere total pressure is a reference point and does not imply that the total pressure of the reaction must be operated at atmospheric pressure. For example, in a mixture of one mol of butene, three mols of steam, and one mol of oxygen under a total pressure of one atmosphere, the butene would have an absolute pressure of one-fifth of the total pressure, or roughly six inches of mercury absolute pressure. Equivalent to this six inches of mercury butene absolute pressure at atmospheric pressure would be butene mixed with oxygen under a vacuum such that the partial pressure of the butene is 6 inches of mercury absolute. The combination of a diluent such as nitrogen, together with the use of a vacuum may be utilized to achieve the desired partial pressure of the hydrocarbon. For the purpose of this invention, also equivalent to the six inches of mercury butene absolute pressure as atmospheric pressure would be the same mixture of one mol of butene, three mols of steam and one mol of oxygen under a total pressure greater than atmospheric, for example, a total pressure of 20 p.s.i.a. Thus, when the total pressure in the reaction zone is greater than one atmosphere, the absolute values for the pressure of the hydrocarbon to be dehydrogenated will be increased in direct proportion to the increase in total pressure above one atmosphere.

The partial pressures described above may be maintained by the use of diluents such as nitrogen, helium or other gases. Conveniently, the oxygen may be added as air with the nitrogen acting as a diluent for the system. Mixtures of diluents may be employed. Volatile compounds which are not dehydrogenated or which are dehydrogenated only to a limited extent may be present as diluents.

Preferably the reaction mixture contains a quantity of steam, with the range generally being between about 2 and 40 mols of steam per mol of hydrocarbon to be dehydrogenated. Preferably steam will be present in an amount from about 3 to 35 mols per mol of hydrocarbon to be dehydrogenated and excellent results have been obtained within the range of about 5 to about 30 mols of steam per mol of hydrocarbon to be dehydrogenated. The functions of the steam are several-fold, and the steam does not merely act as a diluent. Diluents generally may be used in the same quantities as specified for the steam. Excellent results are obtained when the gaseous composition fed to the reactor consists essentially of hydrocarbons, inert diluents and oxygen as the sole oxidizmg agent.

The gaseous reactants may be conducted through the reaction chamber at a fairly wide range of flow rates. The optimum flow rate will be dependent upon such variables as the temperature of reaction, pressure, particle size, and whether a fluid bed or fixed bed reactor is utilized. Desirable flow rates may be established by one skilled in the art. Generally, the flow rates will be within the range of about 0.10 to 25 liquid volumes of the hydrocarbon to be dehydrogenated per volume of reactor containing catalyst per hour (referred to as LHSV), wherein the volumes of hydrocarbon are calculated at standard conditions of 25 C. and 760 mm. of mercury. Usually, the LHSV will be between 0.15 and about 5 or 10. For calculation, the volume of reactor containing catalyst is that volume of reactor space including the volume displaced by the catalyst. For example, if a reactor has a particular volume of cubic feed or void space, when that void space is filled with catalyst particles, the original void space is the volume of reactor containing catalyst for the purpose of calculating the flow rate. The gaseous hourly space velocity (GHSV) is the volume of the hydrocarbon to be dehydrogenated in the form of vapor calculated under standard conditions of 25 C. and 760 mm. of mercury per volume of reactor space containing catalyst per hour. Generally, the GHSV will be between about 25 and 6400, and excellent results have been between about 38 and 3800. Suitable contact times are, for example, from about 0.001 or higher to about 5 or 10 seconds, with particularly good results being obtained between 0.01 and 3 seconds. The contact time is the calculated dwell time of the reaction mixture in the reaction zone, assuming the mols of product mixture are equivalent to the mols of feed mixture. For the purpose of calculation of residence times, the reaction zone is the portion of the reactor containing catalyst.

The catalytic surface described is the surface which is exposed in the dehydrogenation zone to the reactor, that is, if a catalyst carrier is used, the composition described as a catalyst refers to the composition of the surface and not to the total composition of the surface coating plus carrier. The iron, phosphorus and at least one metal from the group consisting of magnesium, zinc, cobalt and nickel will be present as an intimate combination of the ingredients. Catalyst binding agents or fillers may be used, but these will not ordinarily exceel about 50 percent or 60 percent by weight of the catalytic surface. These binding agents and fillers will preferably be essentially inert. The quantity of catalyst utilized will be dependent upon such variables as the temperature of reaction, the concentration of oxygen, the age of the catalyst, and the flow rates of the reactants. The catalyst will be definition be present in a catalytic amount and generally the ferrite together with any defined atoms not combined as the ferrite will be the main active constituents. The amount of catalyst will ordinarily be present in an amount greater than square feet of catalyst surface per cubic foot of reaction zone containing catalyst. Of course, the amount of catalyst may be much greater, particularly when irregular surface catalysts are used. When the catalyst is in the form of particles, either supported or unsupported, the amount of catalyst surface may be expressed in terms of the surface area per unit weight of any particular volume of catalyst particles. The ratio of catalytic surface to weight will be dependent upon various factors, including the particle size, particle size distribution, apparent bulk density of the particles, amount of active catalyst coated on the carrier, density of the carrier, and so forth. Typical values for the surface to weight ratio are such as about one-half to 200 square meters per gram, although higher and lower values may be used. The catalyst is autoregenerative and the process is continuous.

The catalysts may be prepared in a number of ways. The iron, phosphorus and at least one metal from the group magnesium, zinc, nickel and cobalt may be incorporated using starting compounds such as oxides, nitrates, hydroxides, hydrates, carbonates, acetates, halides and so forth. Excellent catalysts are obtained by using salts of the elements. The phosphorus may be incorporated by way of e.g. ortho-phosphoric acid, meta-phosphoric acid, pyrophosphoric acid, phosphorus pentoxide, methyl phosphate, amine phosphate, magnesium phosphate, nickel phosphate, zinc phosphate, cobalt phosphate, iron phosphate, phosphorus oxychloride and so forth.

One method for the preparation of the catalysts is to mix a ferrite e.g. nickel ferrite, with a solution of orthophosphoric acid. The resulting slurry can then be dried and pelleted or coated on a carrier and then dried. Another method is to mix the dry ingredients, other than the phosphorus, with a phosphorus compound such as phosphoric acid or an ammonium phosphate solution and thereafter extrude the damp powder. The ingredients may be dry mixed and compressed into tablets. If the iron is present in the preferred manner, that is, predominantly as a ferrite, the ferrite may be formed in situ on a carrier and the phosphorus added at various stages of the preparation. However, one of the preferred catalysts is a catalyst in the form of unsupported catalyst particles, such as extruded cylindrical pellets.

If a carrier is utilized, the amount of catalytic composition on the carrier will generally be within the range of about 5 to 75 weight percent of the total weight of the active catalytic material plus the carrier. Conventional carriers may be employed such as the aluminas, pumice, silicon carbide and so forth.

The dehydrogenation reactor may be of the fixed bed or fluid bed type. Conventional reactors for the production of unsaturated hydrocarbons are satisfactory. Excellent results have been obtained by packing the reactor with catalyst particles as the method of introducing the catalytic surface. The catalyst is autoregenerative and the process may be continuous. Moreover, small amounts of tars and polymers are formed as compared to some prior art processes.

The atoms of iron will preferably be present in an amount from about 40 to 90 weight percent, based On the total weight of the atoms of iron and the metals selected from the group consisting of magnesium, zinc, nickel and cobalt in the catalyst surface. Particularly preferred are catalysts having a weight percent of iron from or about to 80 percent by weight iron based on the total weight of atoms of iron and the metals selected from the group consisting of magnesium, zinc, nickel and cobalt. Valuable catalysts were produced comprising 'as the main active constituents iron, phosphorus, and at least one metal selected from the group consisting of magnesium, zinc, nickel and cobalt and oxygen in the catalytic surface exposed to the reaction gases. Particularly preferred are catalysts having a catalytic surface consisting essentially of iron, phosphorus, oxgen, and at least one element selected from the group consisting of magnesium, zinc, nickel and cobalt. High yields of product are obtained with catalysts having iron as the predominant metal in the catalytic surface. Preferably there will be at least 25 weight percent of one or more of the metals magnesium, zinc and/or nickel based on the weight of the atoms of iron. Suitable catalysts may contain less than 5 weight percent sodium and/or potassium based on the weight of the iron, and may contain less than 2 weight percent of these atoms.

Preferably at least about 50 and generally at least about weight percent of the atoms of the iron, magnesium, zinc, nickel and cobalt will be present as a ferrite. Included in the definition of ferrites are the active intermediate oxides 'and the reduced ferrites. The preferred ferrite has a cubic face-centered crystal structure. Ordinarily the ferrite will not be present in the most highly oriented crystalline structure, because it has been found that superior results may be obtained with catalysts wherein the ferrite is relatively disordered, that is where there are defects in the crystalline structure. The desired catalyst may be obtained by conducting the reaction to form the active catalyst at relatively low temperatures, that is, at temperatures lower than some of the very high temperatures used for the formation of ferrites prepared for semiconductor applications. Generally the temperature of reaction for the formation of the catalyst comprising ferrites will be less than 1300 C. and preferably less than 1150 C. Of course, under certain conditions momentary temperatures above these temperatures might also be permissible. The reaction time at the elevated temperature in the formation of the catalyst may preferably be from about five minutes to four hours at elevated temperatures high enough to cause formation of the ferrite but less than about 1150 C. Any iron not present in the form of ferrite will desirably be present predominantly as gamma iron oxide. The alpha iron oxide will preferably be present in an amount of no greater than 40 weight percent of the catalytic surface, such as no greater than about 30 weight percent.

Suitable preferred ferrites to be modified with phosphorus according to this invention are zinc ferrites having X-ray diffraction peaks within the d-spacings 4.83 to 4.89, 2.95 to 3.01, 2.51 to 2.57, 2.40 to 2.46, 2.08 to 2.14, 1.69 to 1.75, 1.59 to 1.65, and 1.46 to 1.52, with the most intense peak being between 2.95 to 3.01; magnesium ferferrites having peaks between 4.80 to 4.86, 2.93 to 2.99, 2.49 to 2.55, 2.06 to 2.12, 1.68 to 1.73, 1.58 to 1.63 and 1.45 to 1.50 with the most intense peak being between 2.49 and 2.55; and nickel ferrites having peaks within the d-spacings of 4.79 to 4.85, 2.92 to 2.98, 2.48 to 2.54, 2.05

to 2.11, 1.57 to 1.63 and 1.44 to 1.49, with the most intense peak being within 2.48 to 2.54. The zinc ferrites will generally have peaks within the d-spacings 4:84 to 4.88, 2.96 to 3.00, 2.52 to 2.56, 2.41 to 2.45, 2.09 to 2.13, 1.70 to 1.74, 1.60 to 1.64 and 1.47 to 1.51. Similarly, the magnesium fer-rites will generally have peaks within the dspacings of 4.81 to 4.85, 2.93 to 2.98, 2.50 to 2.54, 2.07 to 2.11, 1.69 to 1.72, 1.59 to 1.62 and 1.46 to 1.49, with the most intense peak being within the range of 2.50 and 2.54. The nickel ferrites will generally have peaks within the d-spacings 4.80 to 4.84, 2.93 to 2.97, 2.50 to 2.53, 2.07 to 2.10, 1.59 to 1.61 and 1.46 to 1.49, with the most intense peaks being within 2.50 to 2.53.

Although excellent results are obtained with the catalysts of this invention with a feed containing only the hydrocarbon, oxygen and perhaps steam or a diluent, it is one of the advantages of this invention that halogen may also be added to the reaction gases to give excellent results. The addition of halogen to the feed is particularly effective when the hydrocarbon to be dehydrogenated is saturated.

The source of halogen fed to the dehydrogenation zone may be either elemental halogen or any compound of halogen which would liberate halogen under the conditions of reaction. Suitable sources of halogen are such as hydrogen iodide, hydrogen bromide and hydrogen chloride; aliphatic halides such as ethyl iodide, methyl bromide, 1,2-dibromo ethane, ethyl bromide, amyl bromide and ally] bromide; cycloaliphatic halides such as cyclohexylbromide; aromatic halides such as benzyl bromide; halohydn'ns such as ethylene bromohydrin; halogen substituted aliphatic acids such as bromoacetic acid; ammonium iodide; ammonium bromide; ammonium chloride; organic amine halide salts such as methyl amine hydrobromide; and the like. Mixtures of various sources of halogen may be used. The preferred sources of halogen are iodine, bromine and chlorine and compounds thereof such as hydrogen bromide, hydrogen iodide, hydrogen chloride, ammonium bromide, ammonium iodide, ammonium chloride, alkyl halides of one to six carbon atoms and mixtures thereof, with the iodine and bromine compounds being particularly preferred, and the best results having been obtained with ammonium iodide, bromide or chloride. When terms such as halogen liberating materials or halogen materials are used in the specification and claims, this includes any source of halogen such as elemental halogens, hydrogen halides or ammonium halides. The amount of halogen, calculated as elemental halogen, may be as little as about 0.0001 or less mol halogen per mol of the hydrocarbon compounds to be dehydrogenated to as high as 0.2 or 0.5 or higher. The preferred range is from about 0.001 to 0.09 mol of halogen per mol of the hydrocarbon to be dehydrogenated to as high as 0.2 to 0.5 or higher. The preferred range is from about 0.001 to 0.09 mol of halogen per mol of the hydrocarbon to be dehydrogenated.

Improved catalysts may be obtained by reducing the catalyst of the invention. The reduction of the catalyst may be accomplished prior to the initial dehydrogenation, or the catalyst may be reduced after the catalyst has been used. It has been found that a used catalyst may be regenerated by reduction and, thus, even longer catalyst life obtained. The reduction may be accomplished with any gas which is capable of reducing iron oxide to a lower valence such as hydrogen, carbon monoxide or hydrocarbons. Generally the fiow of oxygen will be stopped during the reduction step. In these reduced ferrites the catalysts may contain a lower amount of oxygen than the original ferrite. The temperature of reduction may be varied but the process is most economical at temperatures of at least about 200 C., with the upper limit being about 750 C. or 900 C. or even higher under certain conditions.

In the following examples will be found specific embodiments of the invention and details employed in the practice of the invention. Percent conversion refers to the mols of hydrocarbon consumed per mols of hydrocarbon fed to the reactor, percent selectivity refers to the mols of product formed per 100 mols of hydrocarbon consumed, and percent yield refers to the mols of product formed per mol of hydrocarbon fed.

EXAMPLE 1 The catalyst contained magnesium ferrite modified with phosphorus. The magnesium ferrite was Columbian Carbon Company magnesium ferrite type EG-l. The magnesium ferrite had X-ray diffraction peaks at d-spacings with the ranges of 4.81 to 4.85, 2.93 to 2.98, 2.50 to 2.54, 2.07 to 2.11, 1.69 to 1.72, 1.59 to 1.67, and 1.46 to 1.49 with the most intense peak falling Within 2.50 to 2.54. 5 pounds of the magnesium ferrite was spread out on a porcelain drying tray and moistened with 1 liter of water containing 30 cc. of 86 percent by weight orthophosphoric acid (86 percent acid based on the 30 cc.). The damp powder was mixed by hand and screened through a 6 mesh sieve. The composition was then formed into cylindrical pellets having a i -inch diameter by extruding the composition in a pellet mill. The pellets were dried at 100 C. overnight and then heated for 2 hours at 600 C. These pellets were hard and durable. Phosphoric acid was present in the final composition in an amount of 2 weight percent base on the total weight of the composition. The dry pellets were screened to separate the short and long pellets and to retain a size out having a length of from to of an inch. cc. of this catalyst was placed in a reactor tube for testing. The reactor tube was a 1 inch diameter IPS stainless steel reactor. The length of the reactor tube was 20 inches. Into the bottom of the reactor was placed 2 inches of inert ceramic Vycor 6 mm. x 6 mm. Raschig rings. On top of the 125 cc. of catalyst (about a 10 inch deep catalyst section) was placed 6 inches of the same type of Raschig rings. The cold reactor containing the cataiyst was purged with nitrogen and brought from room temperature to approximately 510 C. in hydrogen and held at this temperature for 2 hours. At this time the hydrogen was cut off and a flow stream was introduced into the reactor while the reactor temperature was cooled to 375 C. A butene-Z composition, having a minimum of 98 mol percent butene-2, was then fed over the catalyst at a flow rate of 1.25 liquid hourly space velocity, based on the 125 cc. of catalyst bed. Oxygen was then added to the reactor as air in an amount equivalent to 0.65 mol of oxygen per mol of butene-2. Steam was also present in an amount of 15 mols per mol of butene-2. After 24 hours on stream, the inlet temperature was 300 C. and the maximum temperature in the reactor was 540 C. Under these conditions, the conversion of the butene-2 was 68 mol percent, the selectivity to butadiene was 91 mol percent for a yield of 62 mol percent per pass, based on the butene-2 fed to the reactor. After 800 hours of reaction, the conversion was 70 mol percent, the selectivity was 91 mol percent and the yield of butadiene was 63 mol percent. At an inlet temperature of 365 C. and a maximum temperature in the reactor of 545 C. these values were obtained at the same mol ratio of 15 mols of steam to butene-Z and at the ratio of oxygen to butene-Z of 0.65. The reaction was stopped after 800 hours of operation.

EXAMPLE 2 Butene-2 was dehydrogenated using a magnesium ferrite catalyst which did not contain phosphorus. 5 pounds of the same magnesium ferrite used in Example 1 was spread out on a porcelain drying tray and moistened with 1 liter of distilled water. The damp powder was mixed by hand and screened through a 6 mesh sieve. The powder was then pelleted as in Example 1 and the pellets were dried at 100 C. overnight and heated for 2 hours at 600 C. After 24 hours of operation under the same conditions as in Example 1 the initial temperature was 370 C.

and the maximum temperature was 500 C. Under these conditions, the conversion was 62 mol percent, the selectivity to butadiene was 92 mol percent, and the yield was 57 mol percent per pass. After 168 hours of operation, under these same conditions, the conversion had dropped to 51 mol percent, the selectivity had dropped to 88 mol percent for a yield of 45 mol percent per pass. These values were taken while the inlet temperature was 350 C. and the maximum temperature in the reactor was 530 C. After 168 hours, the reaction was stopped.

EXAMPLE 3 The catalyst was prepared containing 90 weight percent Columbian Carbon magnesium ferrite, type EG-l, and 10 percent by weight of H PO The catalytic composition was coated onto 4 to 5 mesh inert carrier particles in an amount of 30 percent by weight of the total weight. After loading the catalyst into the reactor, the catalyst was maintained in a hydrogen atmosphere for two hours at a temperature of 510 C. Butene-Z was dehydrogenated at a fiow rate of 1 liquid hourly space velocity, steam was included in the composition fed to the reactor in an amount of 30 mols of steam per mol of butene-2 and oxygen was present as air in an amount equivalent to 0.80 mol of per mol of butene-2. The maximum temperature in the reactor was about 540 C. After 48 hours of operation, the conversion was 74 mol percent, the selectivity was 92 mol percent and the yield of butadiene-1,3 was 68 mol percent.

EXAMPLE 4 Butene-2 was dehydrogenated with a magnesium ferrite catalyst modified by phosphorus. The catalyst was not reduced with hydrogen prior to the run. The catalyst contained 2 percent by weight H PO with the remainder being magnesium ferrite, type EG-l. This active composition was coated onto 4 to 5 mesh carrier particles in an amount of 30 percent by weight of the catalytic composition. The reactor containing the catalyst was first heated from room temperature to 260 C. in air. The reactor was then heated with steam being fed to the reactor to a temperature of about 290 C.; during this time the air was not being fed. At the temperature of 290 C., the butene-2 was introduced to the reactor and the air was also introduced. The flow rate was 1 liquid hourly space velocity and oxygen was fed as air in an amount equivalent to 0.70 mol of oxygen per mol of butene-2. Steam was fed in an amount of 30 mols of steam per mol of butene-2. The reactor was heated about 620 C. over a period of 2 hours. The reactor was then slowly cooled to about 550 C. After 20 hours of operation, the conversion was 73 mol percent and the selectivity was 93 mol percent at a maximum temperature in the reactor of about 550 C.

EXAMPLE 5 The catalyst utilized was a ferrite containing iron, magnesium and cobalt modified by phosphorus. 178 grams of yellow iron oxide and 32 grams of magnesium oxide were mixed in 700 m1. of distilled water, ball-milled for 16 hours and filtered. Cobalt nitrate hydrate, 29 grams, and 2.3 grams of magnesium chloride hydrate were dissolved in 50 ml. distilled water. This solution was added to the filtered mixture of oxides and the combination was stirred for 30 minutes. A heavy paste was obtained which was dried in an oven at 105 C. for 16 hours. The dried material was heated at 900 C. for 60 minutes in order to form the ferrite. After cooling, the ferrite composition was reslurried in distilled water and H PO was added in an amount equivalent to 2 percent by weight of 85 percent H PO based on the weight of the ferrite. Alumina catalyst supports, 4 to 6 mesh AMC, were then added. The coated catalyst particles were then re-dried and loaded into a dehydrogenation reactor. A 10 inch catalyst bed was employed in a 1 inch diameter reactor tube. Butene-Z was dehydrogenated to butadiene- 1,3. The flow rate of butene-2 was 1 liquid hourly space velocity. Steam was fed in an amount of 15 mols of steam per mol of butene-Z, and oxygen was fed as air in an amount equivalent to 0.68 mol of 0 per mol of butene-Z. After 3 days of operation, the conversion was 68, the selectivity was 93 and the yield of butadiene-1,3 was 63 mol percent.

EXAMPLE 6 The catalyst contained a combination magnesium ferrite and zinc ferrite composition modified with phosphorus. The magnesium ferrite was the same type EG1 used in the above examples. The zinc ferrite was Columbian Carbon Company type EG-2 having X-ray diffraction peaks at d-spacings within 4.83 to 4.89, 2.95 to 3.01, 2.51 to 2.57, 2.40 to 2.46, 2.08 to 2.14, 1.69 to 1.75, 1.59 to 1.65, and 1.46 to 1.52, with the most intense peak being between 2.95 to 3.01. The X-ray determinations were run with a cobalt tube. The catalyst was prepared by mixing 5 weight percent of the zinc ferrite with 95 percent by weight of the magnesium ferrite in an aqueous slurry of distilled Water. To this composition was added 2 percent by weight of percent H PO aqueous solution based on the total weight of the zinc ferrite and magnesium ferrite. After this composition had been thoroughly mixed, alumina carrier, type SA 5218, was added and the catalytic composition was coated on the carrier. The carrier particles were inch in diameter. After the catalyst was loaded into the reactor, hydrogen was passed through the reactor for about 2 hours with the catalyst temperature being about 500 C. Butene-2 was dehydrogenated to butadiene-1,3 at a flow rate of 1.0 liquid hourly space velocity, 0.63 mol of oxygen fed as air per mol of butene-2 and 15 mols of steam per mol of butene-Z. After 25 hours of operation, the yield of butadiene was 58 mol percent at a maximum temperature in the reactor of 515 C.

EXAMPLE 7 The procedure in Example 6 was repeated with the exception that 10 percent by weight zinc ferrite was utilized instead of the 5 percent of Example 6. After 119 hours of operation the yield of butadiene was 63 mol percent at a maximum temperature in the reactor of 555 C. After 141 hours of operation, the catalyst was reactivated by burning off the coke and reducing the catalyst with hydrogen for 2 hours at a temperature of about 510 C. After 382 hours of operation the catalyst was still producing butadiene at a yield of 60 mol percent.

EXAMPLE 8 The procedure of Example 6 was repeated with the exception that the catalyst contained 25 percent by weight of the zinc ferrite based on the total weight of zinc ferrite and magnesium ferrite. After 200 hours of operation, the yield of butadiene was greater than 60 mol percent at a reactor temperature of 510 C.

EXAMPLE 9 The catalyst contained iron, magnesium, nickel and phosphorus. 178 grams of Fe O type YLO, plus 37.2 grams of MgCO and 29 grams of Ni(NO -6H O were thoroughly mixed and slurried in distilled water. This composition was reacted at 900 C. for about 60 minutes to form the ferrite. After cooling, the catalytic composition was again slurried in distilled water and 2 percent by weight of an 85 percent aqueous slurry of H PO was added, based on the weight of the iron, magnesium and nickel compounds utilized. Thereafter, a 4 -inch diameter catalyst carrier, type SA 5218, was added in an amount to produce a 25 percent by weight active catalyst. Butene-2 was dehydrogenated utilizing l5 mols of steam and 0.65 mol of O fed as air per mol of butene-2. The flow rate was 1.0 LHSV. After 50 hours of operation, the yield of butadiene was greater than 60 mol percent.

Another feature of this invention is in the use of catalysts modified with silicon in addition to phosphorus. Catalysts of high selectivity have been produced by such a combination. These catalysts also possess other important features such as the long life set forth above. There apparently is some synergistic effect resulting from the combination of phosphorus and silicon in the catalyst. The silicon may be added at any stage of the catalyst preparation, but it generally will be added in such amount that intimate mixing with the other ingredients is insured. One suitable method of preparation is to add the silicon in the form of silica, SiO Silica may be incorporated in the catalyst, for example, by the acid hydrolysis of an organic or inorganic silicate, such as tetraethyl ortho silicate or sodium silicate. The resulting hydrogel may be slurried with the other catalytic ingredients. If the starting material is sodium silicate ordinarily the solution formed by acid hydrolysis will be filtered and washed to remove extraneous ions before combining with the other catalytic compositions. Another method of preparation is to mix a silicate, ferrite and a source of phosphorus in aqueous media whereby the silicate hydrolyzes in the presence of the other components of the catalyst. The silicon may also be added as finely ground and dried silica which may be added to the other components of the catalyst. Regardless of the method of preparation the silicon should be present in an intimate combination with the other catalytic components such as phosphorus, iron and at least one metal selected from the group consisting of magnesium, zinc, cobalt and nickel.

The silica, if employed, will preferably be present in an amount from .003 to 0.30 atom of silicon per atom of iron in the catalyst, but preferably will be present in an amount of .005 to 0.20 atom of silicon per atom of iron.

EXAMPLE 10 A catalyst was prepared having magnesium ferrite modified with both phosphorus and silicon. The catalyst was prepared by the same general procedure as used in Example 4. However, during the coating operation silicon was added as SiO through acid hydrolysis of ethyl silicate. The final catalyst consisted of the same magnesium ferrite used in Example 1 together with 2 percent by weight H PO and 10 percent by weight Si based on the total weight of the magnesium ferrite, H PO and SiO This composition was coated on inert alumina carriers type AMC, size 4 to 5 mesh. Prior to operation, the reactor containing the catalyst was purged at room temperature with nitrogen and thereafter hydrogen was introduced at 500 cc. per minute (STP). The reactor in a hydrogen atmosphere was then held at 570 for a period of two hours. Thereafter the reactor was cooled to 370 C. and purged with methane. Next, the steam, butene-2 and air flows were begun. Butene-Z was fed at a rate of 1 liquid hourly space velocity. Steam was employed in an amount of 30 mols of steam per mol of butene-2 and oxygen was present in an amount of 0.80 mol of oxygen per mol of butene-2, fed as air.

After 510 hours of operation, the yield was greater than 52 mol percent. The catalyst was then reduced in hydrogen in the same manner as for the original start-up, the conversion then increased to 68 mol percent and the selectivity increased. These values held over the next 355 hours of operation.

The catalysts of this invention will be used in the form of inorganic oxides for the dehydrogenation reaction. This definition means that the catalysts are inorganic and contain oxygen; included in this definition are the ferrites. However, as pointed out, the catalysts may be produced from organic precursors such as the acetates or oxalates.

Although the compositions of this invention have particularly been described for use as catalysts for dehydrogenation reactions the compositions have other uses. For example, the compositions are useful as catalysts for other types of reactions. Also the compositions are useful as pigments wtih the presence of the phosphorus contributing to these excellent pigments. The compositions are generally useful where ferrite pigments such as magnesium ferrite has been employed.

I claim:

1. A composition of matter comprising phosphorus and a member selected from the group consisting of ferrites of magnesium, zinc, cobalt, nickel and mixtures thereof wherein the phosphorus is present in an amount of from .002 to 0.35 atom of phosphorus per atom of iron in the said ferrite and the atoms of magnesium, zinc, cobalt and nickel are present in a total amount of from .05 to 2 atoms per atom of iron.

2. The composition of claim 1 wherein the said composition contains less than 5 weight percent of a member selected from the group consisting of sodium, potassium and mixtures thereof based on the weight of the said iron.

3. A composition of matter comprising phosphorus and a ferrite selected from the group consisting of magnesium ferrite, zinc ferrite, cobalt ferrite, nickel ferrite and mixtures thereof wherein the phosphorus is present in an amount of from .002 to 0.25 atom of phosphorus per atom of iron and the atoms of magnesium, zinc, cobalt and nickel are present in a total amount of from .2 to 1.0 atom per atom of iron.

4. A composition of matter comprising magnesium ferrite and phophorus in intimate combinations wherein the phosphorus is present in an amount from about .002 to 0.25 atom of phosphorus per atom of iron, the said magnesium ferrite having X-ray diffraction peaks and d-spacings within the ranges of 4.80 to 4.86, 2.93 to 2.99, 2.49 to 2.55, 2.06 to 2.12, 1.68 to 1.73, 1.58 to 1.63, and 1.45 to 1.50, with the most intense peak being between 2.49 to 2.55.

5. A composition of matter comprising nickel ferrite and phosphorus in intimate combinations wherein the phosphorus is present in an amount from about .220 to 0.25 atom of phosphorus per atom of iron.

6. A composition of matter comprising phosphorus and a member selected from the group consisting of ferrites of magnesium, zinc, cobalt, nickel and mixtures thereof wherein the phosphorus is present in an amount of from .002 to 0.25 atom of phosphorus per atom of iron in the said ferrite and the atoms of magnesium, zinc, cobalt and nickel are present in a total amount of from .05 to 2 atoms per atom of iron in the said ferrite and wherein the atoms of iron are present in an amount of about 40 to weight percent of the said composition.

7. A composition of matter consisting essentially of iron, phosphorus, oxygen and at least one member s lected from the group consisting of magnesium, Zinc, nickel, cobalt and mixtures thereof and wherein the said iron is predominately present in a ferrite structure.

8. A composition of matter comprising zinc ferrite and phosphorus in intimate combinations wherein the phos phorus is present in an amount from about .002 to 0.25 atom of phosphorus per atom of iron, the said ferrite having X-ray diffraction peaks and d-spacings within the ranges of 4.84 to 4.88, 2.96 to 3.00, 2.52 to 2.56, 2.41 to 2.45, 209 to 2.13, 1.70 to 1.74, 1.60 to 1.64 and 1.47 to 1.51, with the most intense peak being between 2.96 to 3.00.

9. A composition of matter comprising magnesium ferrite and phosphorus wherein the phosphorus is present in an amount of from .005 to 0.20 atom of phosphorus per atom of iron and wherein the atoms of iron are present in an amount of about 40 to 90 weight percent of said catalyst and wherein the said magnesium ferrite has been formed at a temperature of no greater than about 1150 C.

10. A ferrite composition of matter comprising phosphorus, silicon and a member selected from the group consisting of magnesium, zinc, cobalt, nickel and mixtures thereof wherein the phosphorus is present in an amount of from .002 to 0.25 atom of phosphorus per atom of iron and the atoms of magnesium, zinc, cobalt and nickel are present in a total amount of from .05 to 2 atoms per atom of iron and wherein the atoms of silicon are present in an amount of about .003 to 0.30 atom of silicon per atom of iron.

11. A composition of matter comprising iron in the form of a material selected from the group consisting of the ferrites of metals selected from the group consisting of magnesium, zinc, cobalt and nickel and mixed fer-rites containing two or more metals selected from the group consisting of magnesium, zinc, nickel and cobalt and phosphorus added to the composition in the form of a material selected from the group consisting of a phosphoric acid, a phosphorus oxide, a phosphate, and mixtures, said phosphorus being present in an amount of 0.002 to 0.25 atom of phosphorus per atom of iron.

12. The composition of claim 11 wherein the phosphorus has been added as an inorganic metal phosphate, wherein the metal of the said phasphate is selected from the group consisting of magnesium, zinc, cobalt and nickel.

13. A a composition of matter comprising iron in the form of a material selected from the group consisting of the ferrites of metals selected from the group consisting of magnesium, zinc, cobalt and nickel and mixed ferrites containing tWo or more metals selected from the group consisting of magnesium, zinc, nickel and cobalt and phosphorus added to the composition in the form of phosphoric acid, said phosphorus being present in an amount of 0.002 to 0.25 atom of phosphorus per atom of iron, said composition having been reduced with a reducing gas.

14. A composition of matter comprising a combination of phosphorus and a member selected from the group consisting of ferrites of magnesium, zinc, cobalt, nickel and mixtures thereof wherein the phosphorus is present in an amount of from .002 to 0.25 atom of phosphorus per atom of iron in the said ferrite and the atoms of magnesium, Zinc, cobalt and nickel are present in a total amount of from 0.5 to 2 atoms per atom of iron in the said ferrite and wherein the said combination has been formed by heating the ingredients at a temperature high enough to form a ferrite but no greater than 1150 C.

and nickel are present in a total amount of from .2

to 1.0 atom per atom of iron in the said ferrite, the atoms of iron are present in an amount of about to weight percent of the said composition and wherein the said ferrite has been formed at a temperature of less than 1150 C. and thereafter the composition has been reduced with a reducing gas selected from the group consisting of hydrogen, carbon monoxide or hydrocarbons at at temperature from about 200 C. to about 900 C.

References Cited UNITED STATES PATENTS 2,442,131 5/1948 Kearby 252-473 2,888,499 5/1959 Pitzer et al 252-473 3,100,234 8/1963 Lee 252-473 3,270,080 8/1966 Christmann 260-680 PATRICK P. GARVIN, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,398,100 August 20, 1968 Harold F. Christmann It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, lines 7 and 8, "phophorun" should read phosphorus line 41, "2-methylphentene-l" should read 2- methylpentene-l Column 4, line 59, "or" should read of Column 5, line 13, "exceel" should read exceed line 19, "he" should read by Column 8, line 42, after "flow" insert of Column 9, line 48, after "heated" insert to Column 10, line 71, "actives" should read active Column 12, line 2, "wtih" should read with line 61, "209" should read 2.09 Column 13, line 4, "0.30" should read .030 line 21, "A a" should read A Column 14, line 3, "0.5" should read .05

Signed and sealed this 24th day of February 1970. (SEAL) Attest:

Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents 

